Solvent composition, cleaning method, method of forming a coating film, heat transfer fluid, and heat cycle system

ABSTRACT

There are provided a solvent composition which is excellent in solubility of various organic substances and excellent in detergency and a drying property, and has no adverse effect on a global environment and is excellent in stability; a cleaning method using the solvent composition; a method of forming a coating film; a heat transfer fluid including the solvent composition; and a heat cycle system using the heat transfer fluid. A solvent composition including 1-chloro-2,3,3-trifluoro-1-propene and 1-chloro-3,3-difluoro-1-propyne, a cleaning method of bringing the solvent composition and an article into contact with each other, a method of dissolving a nonvolatile organic compound in the solvent composition to produce a coating film-forming composition and evaporating the solvent composition after applying the coating film-forming composition on an article to be coated, to form a coating film, a heat transfer fluid including the solvent composition, and a heat cycle system using the heat transfer fluid.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of U.S. application Ser.No. 15/865,463, filed Jan. 9, 2018, which is in turn a continuation ofprior International Application No. PCT/JP2016/062475, filed on Apr. 20,2016 which is based upon and claims the benefit of priority fromJapanese Patent Applications No. 2015-148070, filed on Jul. 27, 2015 andNo. 2016-005952, filed on Jan. 15, 2016; the entire contents of all ofwhich are incorporated herein by reference.

FIELD

The present invention relates to a solvent composition which isexcellent in solubility of various organic substances and excellent indetergency and has a sufficient drying property, and has no adverseeffect on a global environment and is excellent in stability.Specifically, the solvent composition of the present invention can beused in a wide range of uses, such as a cleaning solvent, a dilutioncoating solvent, and a heat transfer fluid.

BACKGROUND

In manufacture of IC, an electronic component, a precision machinerycomponent, an optical component, and the like, in a manufacturingprocess, an assembly process, a final finishing process, and the like,components are cleaned by a cleaning solvent, thereby removing flux, aprocessing oil, wax, a release agent, dust, and the like adhering to thecomponents. Further, as a method of manufacturing an article having acoating film containing various organic chemical substances such as alubricant, for example, there is known a method in which a solution inwhich the organic chemical substances have been dissolved in a dilutioncoating solvent is prepared, the solution is applied on an article to becoated, and thereafter the dilution coating solvent is evaporated toform a coating film. The dilution coating solvent is required to allowthe organic chemical substances to be dissolved sufficiently and to havea sufficient drying property as well.

As a solvent to be used in such uses, in that it has incombustibilityand low toxicity, is excellent in stability, does not encroach on a basematerial of metal, plastic, elastomer, or the like, and is excellent inchemical and thermal stability, there has been used a fluorinatedsolvent or the like containing a chlorofluorocarbon (hereinafter,mentioned as “CFC”) such as 1,1,2-trichloro-1,2,2-trifluoroethane, ahydrochlorofluorocarbon (hereinafter, mentioned as “HCFC”) such as2,2-dichloro-1,1,1-trifluoroethane, 1,1-dichloro-1-fluoroethane,3,3-dichloro-1,1,1,2,2-pentafluoropropane, and1,3-dichloro-1,1,2,2,3-pentafluoropropane, or the like.

However, because the CFCs and the HCFCs are chemically very stable, theyeach have a long lifetime in the troposphere after vaporization, anddiffuse and reach the stratosphere. Therefore, there is a problem thatthe CFCs and the HCFCs which have reached the stratosphere aredecomposed by ultraviolet rays and generate chlorine radicals to depletean ozone layer.

On the other hand, as a solvent having no chlorine atom and having noadverse effect on the ozone layer, a perfluorocarbon (hereinafter,mentioned as “PFC”) is known. In addition, as an alternative solvent tothe CFCs and the HCFCs, a hydrofluorocarbon (hereinafter, mentioned as“HFC”), a hydrofluoroether (hereinafter, mentioned as “HFE”), and thelike are also under development. However, because the HFCs and the PFCshave a high global warming potential, they are substances subject toregulation by the Kyoto Protocol.

As a new solvent substituted for the solvents of the HFCs, the HFEs, andthe PFCs, a fluoroolefin having a double bond between carbon atoms isproposed. Because the fluoroolefin has a short lifetime in theatmosphere due to easy decomposition and its ozone depletion potentialand global warming potential are low, it has an excellent property inwhich an effect on a global environment is small, but on the other hand,it is poor in stability due to the easy decomposition, and there hasbeen a problem that in a case of use as the cleaning solvent or thedilution coating solvent, it decomposes and acidifies in use.

Therefore, in Patent References 1 (JP-A No. 2013-504658) and 2 (JP-A No.2013-506731), there is disclosed a technology of adding additionalcomponents as a lubricant, a stabilizer, a metal passivator, a corrosioninhibitor, a flame inhibitor, and other compound and/or component forregulating a specific property of a composition to a wide variety offluoroolefins which each include 1-chloro-2,3,3-trifluoro-1-propene andeach have a double bond between carbon atoms. However, Patent References1 and 2 do not mention a technology of stabilizing1-chloro-2,3,3-trifluoro-1-propene by adding1-chloro-3,3-difluoro-1-propyne to 1-chloro-2,3,3-trifluoro-1-propene.

SUMMARY

In the present invention, it is an article thereof to provide: a solventcomposition which is excellent in solubility of various organicsubstances and excellent in detergency and has a sufficient dryingproperty, and has no adverse effect on a global environment and isexcellent in stability; a cleaning method using the solvent composition;a method of forming a coating film using the solvent composition; a heattransfer fluid including the solvent composition; and a heat cyclesystem using the heat transfer fluid.

The present inventors have performed studies in consideration of theabove-described points, resulting in completing the present invention.That is, the present invention consists of the following.

[1] A solvent composition including 1-chloro-2,3,3-trifluoro-1-propeneand 1-chloro-3,3-difluoro-1-propyne.

[2] The solvent composition according to [1], wherein a proportion of acontent of 1-chloro-3,3-difluoro-1-propyne to a total of a content ofthe 1-chloro-2,3,3-trifluoro-1-propene and a content of the1-chloro-3,3-difluoro-1-propyne is 0.0001 to 0.1 mass %.

[3] The solvent composition according to [1], wherein a proportion of acontent of 1-chloro-2,3,3-trifluoro-1-propene to a total amount of thesolvent composition is 80 mass % or more.

[4] The solvent composition according to [1], wherein the1-chloro-2,3,3-trifluoro-1-propene consists of(Z)-1-chloro-2,3,3-trifluoro-1-propene and(E)-1-chloro-2,3,3-trifluoro-1-propene, and a proportion of a content of(Z)-1-chloro-2,3,3-trifluoro-1-propene to a total amount of1-chloro-2,3,3-trifluoro-1-propene is 80 to 100 mass %.

[5] A cleaning method including bringing the solvent compositionaccording to [1] and an article to be cleaned into contact with eachother.

[6] The cleaning method according to [5], wherein a processing oiladhering to the article to be cleaned is cleaned.

[7] The cleaning method according to [6], wherein the processing oil isat least one selected from a group consisting of a cutting oil, aquenching oil, a rolling oil, a lubricating oil, a machine oil, apresswork oil, a stamping oil, a drawing oil, an assembly oil, and awire drawing oil.

[8] The cleaning method according to [5], wherein the article to becleaned is clothing.

[9] A method of forming a coating film including dissolving anonvolatile organic compound in the solvent composition according to [1]to prepare a coating film-forming composition and evaporating thesolvent composition after applying the coating film-forming compositionon an article to be coated, to form a coating film consisting of thenonvolatile organic compound.

[10] A heat transfer fluid including the solvent composition accordingto [1].

[11] A heat cycle system using the heat transfer fluid according to[10].

A solvent composition of the present invention is excellent insolubility of various organic substances and excellent in detergency andhas a sufficient drying property, and has no adverse effect on a globalenvironment and is excellent in stability. A cleaning method of thepresent invention has no adverse effect on a global environment and isexcellent in detergency. A method of forming a coating film of thepresent invention has no adverse effect on a global environment andallows a uniform coating film to be formed. A heat transfer fluidincluding the solvent composition of the present invention has noadverse effect on a global environment and is excellent in stability. Aheat cycle system using the heat transfer fluid of the present inventionhas no adverse effect on a global environment.

BRIEF DESCRIPTION OF THE DRAWINGS

The FIGURE is a view schematically illustrating one example of acleaning apparatus carrying out a cleaning method of the presentinvention.

MODE FOR CARRYING OUT THE INVENTION

<Solvent Composition>

A solvent composition of the present invention includes1-chloro-2,3,3-trifluoro-1-propene (CHCl═CF—CHF₂. hereinafter mentionedas “HCFO-1233yd”) and 1-chloro-3,3-difluoro-1-propyne (CCl≡C—CHF₂).

In the solvent composition of the present invention, HCFO-1233yd is acomponent having an excellent property described below as a solvent, and1-chloro-3,3-difluoro-1-propyne is a component included in the solventcomposition as a stabilizer stabilizing HCFO-1233yd.

(HCFO-1233yd)

Because HCFO-1233yd is fluoroolefin having a double bond between carbonatoms, its lifetime in the atmosphere is short and its ozone depletionpotential and global warming potential are low.

In HCFC-1233yd, a Z-isomer and an E-isomer which are a geometric isomerexist according to positions of substituents on the double bond. Whenthe compound name or an abbreviated name of the compound is used unlessotherwise stated in this description, at least one selected from theZ-isomer and the E-isomer is indicated, and when (E) or (Z) is denotedbehind the compound name or the abbreviated name of the compound, an(E)-isomer or a (Z)-isomer of each compound is indicated. For example,HCFO-1223yd(Z) indicates the Z-isomer, and HCFO-1233yd(E) indicates theE-isomer.

A boiling point of HCFO-1233yd(Z) is about 54° C., a boiling point ofHCFO-1233yd(E) is about 48° C., and both are substances excellent in adrying property. Further, even though they are boiled to turn intovapor, even parts susceptible to heat, such as resin parts, are noteasily adversely affected since the boiling point of HCFO-1233yd(Z) isabout 54° C. and the boiling point of HCFO-1233yd(E) is about 48° C. Inaddition, HCFO-1233yd has excellent ability as a cleaning solvent or acoating solvent, such as no flash point, low surface tension andviscosity, and easy evaporation even at a normal temperature.

Note that in this description, the boiling points of the compounds areboiling points at a normal pressure unless otherwise stated. In thisdescription, the normal pressure means 760 mmHg and the normaltemperature means 25° C., respectively.

On the other hand, HCFO-1233yd does not have sufficient stability andwhen HCFO-1233yd is retained at the normal temperature and the normalpressure, it decomposes in several days to generate chlorine ions.Therefore, in the solvent composition of the present invention,stabilization of HCFO-1233yd is achieved by containing thelater-described 1-chloro-3,3-difluoro-1-propyne with HCFO-1233yd.

In the solvent composition of the present invention, a proportion of acontent of HCFO-1233yd is preferably 50 mass % or more, more preferably80 mass % or more and further preferably 90 mass % or more to a totalamount of the solvent composition. As long as the proportion is equal toor more than the above lower limit value, the solvent composition isexcellent in solubility of various organic substances and detergency.The content of HCFO-1233yd is particularly preferably an amount in whicha content of 1-chloro-3,3-difluoro-1-propyne has been removed from thetotal amount of the solvent composition. That is, the solventcomposition particularly preferably consists of only HCFO-1233yd and1-chloro-3,3-difluoro-1-propyne. However, the solvent composition maycontain a component which is produced in a manufacturing process ofHCFO-1233yd and is difficult to separate from HCFO-1233yd and/or acomponent which is produced in a manufacturing process of1-chloro-3,3-difluoro-1-propyne and is difficult to separate from1-chloro-3,3-difluoro-1-propyne in a range in which an effect of thepresent invention is not impaired, for example, by an amount which is 10mass % or less with respect to the total amount of the solventcomposition.

In the solvent composition of the present invention, in the Z-isomer andthe E-isomer of HCFO-1233yd, HCFO-1233yd(Z) is preferable in that it hasthe boiling point higher than that of HCFO-1233yd(E) and does not easilyvolatilize at the normal temperature. Therefore, a proportion of acontent of HCFO-1233yd(Z) to a total amount of HCFO-1233yd is preferably80 to 100 mass %, and more preferably 90 to 100 mass %. As long as theproportion is in the above range, a loss due to volatilization of thesolvent composition is suppressed, which leads to a reduction in usage,thereby being excellent in economic efficiency. However, an upper limitvalue of the proportion of the content of HCFO-1233yd(Z) is particularlypreferably about 99.9 mass % to the total amount of HCFO-1233yd from theviewpoint of suppressing an increase in a manufacturing cost due to adistillation separation of the Z-isomer and the E-isomer of HCFO-1233yd,or the like.

HCFO-1233yd can be manufactured by subjecting, for example, industriallystably obtainable 1-chloro-2,2,3,3-tetrafluoropropane (CHF₂—CF₂—CHFCl,hereinafter, mentioned as “HCFC-244ca”) to a dehydrofluorinationreaction. According to this method, HCFO-1233yd is produced by thedehydrofluorination reaction at temperatures of 50 to 80° C., usingHCFC-244ca as a raw material and using potassium hydroxide or sodiumhydroxide as a reactant.

In the produced HCFO-1233yd, HCFO-1233yd(Z) and HCFO-1233yd(E) which area structural isomer exist, and in this manufacturing method,HCFO-1233yd(Z) is produced more than HCFO-1233yd(E). These isomers canbe separated into HCFO-1233yd(Z) and HCFO-1233yd(E) in a purificationprocess thereafter.

Note that in the solvent composition of the present invention, a roughlypurified product of HCFO-1233yd which is obtained by appropriatelypurifying the reaction solution including HCFO-1233yd produced in theabove and includes the component difficult to separate from HCFO-1233ydother than HCFO-1233yd to such an extent that the effect of the presentinvention is not impaired may be used. If the roughly purified productof HCFO-1233yd is used, a cost of the distillation separation or thelike is reduced, which is preferable.

As the component difficult to separate from HCFO-1233yd which isincluded in the reaction solution which is obtained by theabove-described manufacturing method and includes HCFO-1233yd,HCFC-244ca which is the raw material, or the like can be cited. Aboiling point of HCFC-244ca is about 53° C. and close to the boilingpoint of HCFO-1233yd(Z), and therefore when HCFO-1233yd is used asHCFO-1233yd(Z) or as an isomer mixture of HCFO-1233yd, in particular,HCFC-244ca can be included in the roughly purified product.

When the above-described roughly purified product of HCFO-1233yd isused, a proportion of a content of HCFC-244ca in the solvent compositionis preferably 1 mass % or less to the total amount of the solventcomposition from the viewpoint of an environmental load. Further, ifHCFC-244ca is included in the solvent composition, the proportion of thecontent of HCFC-244ca is preferably 0.0001 to 1 mass %, more preferably0.005 to 1 mass %, and further preferably 0.01 to 0.05 mass % to a totalof the content of HCFO-1233yd and the content of HCFC-244ca from theviewpoint of the environmental load and a separation cost.

(1-chloro-3,3-difluoro-1-propyne)

1-chloro-3,3-difluoro-1-propyne is fluorocarbon having a triple bondbetween carbon atoms, and its ozone depletion potential and globalwarming potential are low. 1-chloro-3,3-difluoro-1-propyne is soluble inHCFO-1233yd.

1-chloro-3,3-difluoro-1-propyne is considered to have a function as astabilizer suppressing decomposition of HCFO-1233yd(Z) andHCFO-1233yd(E) and stabilizing them by an effect which is notnecessarily clear but is presumed to be capture of radicals.

Note that in this description, solubility of a certain substance inHCFO-1233yd means a property capable of dissolving the substanceuniformly without causing a two-layer separation and turbidity by mixingit with HCFO-1233yd and stirring it at the normal temperature (25° C.)so as to become a desired concentration.

Further, the stability in the solvent composition of the presentinvention can be evaluated by, for example, providing a chlorine ionconcentration after retaining the solvent composition for a certainperiod as an index. The solvent composition of the present inventioncontaining 1-chloro-3,3-difluoro-1-propyne with HCFO-1233yd allows thechlorine ion concentration in the solvent composition which is measuredafter retaining the solvent composition at 50° C. for three days to besuppressed to less than 100 ppm, for example. Note that regulating anamount of 1-chloro-3,3-difluoro-1-propyne with respect to HCFO-1233yd inthe solvent composition also makes it possible to set a chlorine iongeneration amount in a case of evaluation similar to that in the aboveto less than 50 ppm or less than 10 ppm.

A content of 1-chloro-3,3-difluoro-1-propyne in the solvent compositionof the present invention is not limited as long as it is an amount inwhich HCFO-1233yd is capable of exhibiting the above-described abilityas a solvent and the stabilization of HCFO-1233yd is kept. A proportionof the content of 1-chloro-3,3-difluoro-1-propyne in the solventcomposition is preferably 0.0001 to 0.1 mass % and more preferably0.0001 to 0.001 mass % to a total of the content of HCFO-1233yd and thecontent of 1-chloro-3,3-difluoro-1-propyne. As long as the proportion isin the above-described range, the stability of the solvent compositionis further excellent.

1-chloro-3,3-difluoro-1-propyne can be manufactured by, for example, thefollowing method (A) or method (B).

The method (A) is a method mentioned in a non-patent document Journal ofFluoro Chem 126 (2005), pages 1549 to 1552. Specifically, it is themethod of manufacturing 1-chloro-3,3-difluoro-1-propyne by subjecting1,2-dichloro-3,3-difluoro-1-propene (CHCl═CCl—CHF₂) to adehydrochlorination reaction using a base as a catalyst.

The method (B) is a method of manufacturing1-chloro-3,3-difluoro-1-propyne by using HCFO-1233yd as a raw materialinstead of 1,2-dichloro-3,3-difluoro-1-propene in the method (A) andsubjecting it to a dehydrofluorination reaction (hereinafter,“dehydrofluorination reaction (2)”). Note that regulating a conditionwhen HCFO-1233yd is manufactured by using HCFC-244ca as the raw materialand subjecting it to the dehydrofluorination reaction (hereinafter,“dehydrofluorination reaction (1)”) allows the dehydrofluorinationreaction (2) to be promoted simultaneously with the dehydrofluorinationreaction (1).

Thus, according to the method (hereinafter, referred to as a method(B′)) in which the dehydrofluorination reaction (1) and thedehydrofluorination reaction (2) are simultaneously promoted usingHCFC-244ca as the raw material, a reaction solution containingHCFO-1233yd and 1-chloro-3,3-difluoro-1-propyne together can beobtained. Regulating a reaction condition in the method (B′) also makesit possible to make a relationship of the content between HCFO-1233ydand 1-chloro-3,3-difluoro-1-propyne in the reaction solution to beproduced similar to a desirable relationship of the content between bothin the solvent composition of the present invention.

Note that 1-chloro-3,3-difluoro-1-propyne is close to HCFO-1233yd,particularly HCFO-1233yd(E) in the boiling point. Accordingly, it isalso possible to separate a mixture which includes HCFO-1233yd and1-chloro-3,3-difluoro-1-propyne together and in which a content of acomponent other than these is reduced to an amount in which the effectof the present invention is not impaired from the reaction solution tobe produced by the method (B′), and it is also possible to use themixture as it is as the solvent composition of the present invention.

In the present invention, in terms of production efficiency,1-chloro-3,3-difluoro-1-propyne is preferably the one to be obtained bythe method (B), and more preferably the one to be obtained by the method(B′).

By the method (B′), HCFO-1233yd and 1-chloro-3,3-difluoro-1-propyne areproduced. From the reaction solution to be obtained by the method (B′),HCFO-1233yd(Z), HCFO-1233yd(E), and 1-chloro-3,3-difluoro-1-propyne maybe each isolated and used for the solvent composition of the presentinvention, or may be used as a mixture including two or more of thesefor the solvent composition.

Here, as described above, HCFO-1233yd(E) and1-chloro-3,3-difluoro-1-propyne are close to each other in the boilingpoint, and purification equipment and purification techniques havinghigh accuracy are required for a separation of both, in particular,isolation of 1-chloro-3,3-difluoro-1-propyne. Accordingly, it ispreferable from the viewpoint of manufacturing cost reduction andproduction efficiency improvement to separate each of a mixture ofHCFO-1233yd(E) and 1-chloro-3,3-difluoro-1-propyne, and HCFO-1233yd(Z)from the reaction solution to be obtained by the method (B′), use these,and regulate the content of each of the components in the solventcomposition of the present invention. Note that since isolation ofHCFO-1233yd(E) is easier compared with the isolation of1-chloro-3,3-difluoro-1-propyne from the reaction solution to beobtained by the method (B′), HCFO-1233yd(E) may be isolated from thereaction solution to be obtained by the method (B′) and used for thesolvent composition of the present invention as necessary.

As the above-described mixture of HCFO-1233yd(E) and1-chloro-3,3-difluoro-1-propyne, for example, the mixture including anamount in which 1-chloro-3,3-difluoro-1-propyne is set to 0.1 to 10 mass% with respect to a total of the content of HCFO-1233yd(E) and thecontent of 1-chloro-3,3-difluoro-1-propyne is preferable in terms of theproduction efficiency improvement.

(Optional Component)

The solvent composition of the present invention may contain components(hereinafter, simply referred to as “other component”) other thanHCFO-1233yd, 1-chloro-3,3-difluoro-1-propyne, and the above-describedcomponent which is produced in the manufacturing process of HCFO-1233ydor 1-chloro-3,3-difluoro-1-propyne and is difficult to separate fromHCFO-1233yd or 1-chloro-3,3-difluoro-1-propyne in the range in which theeffect of the present invention is not impaired. The other componentsmay be components (however, 1-chloro-3,3-difluoro-1-propyne is excluded,and hereinafter, referred to as “other solvent”) which are useddepending on various purposes such as enhancing of the solubility andregulating of an evaporation rate, are soluble in HCFO-1233yd, andfunction as a solvent other than HCFO-1233yd, for example.

The other components may be stabilizers (hereinafter, referred to as“other stabilizer”) other than 1-chloro-3,3-difluoro-1-propynestabilizing HCFO-1233yd, for example.

As the other stabilizers, there can be cited at least one selected froma group consisting of phenols, ethers, epoxides, amines, alcohols, andhydrocarbons. The stabilizer may be one or a combination of two or more.

As the phenols, phenol, 1,2-benzendiol,2,6-di-tert-butyl-4-methylphenol, m-cresol, 2-isopropyl-5-methylphenol,α-tocopherol, and 2-methoxyphenol are preferable.

As the ethers, cyclic ethers having 4 to 6 members are preferable, andamong them, 1,4-dioxane, 1,3-dioxane, 1,3,5-trioxane, 2-methylfuran, andtetrahydrofuran are preferable.

As the epoxides, 1,2-propylene oxide, 1,2-butylene oxide, and butylglycidyl ether are preferable.

As the amines, alkylamine and cyclic amines are preferable, and amongthem, pyrrole, N-methylpyrrole, 2-methylpyridine, n-propylamine,diisopropylamine, N-methylmorpholine, and N-ethylmorpholine arepreferable.

As the alcohols, methanol, ethanol, isopropyl alcohol, and2-propyne-1-ol which are linear or branched-chained alcohols having 1 to3 carbon atoms are preferable.

As the hydrocarbons, regarding saturated hydrocarbons, n-pentane,cyclopentane, n-hexane, cyclohexane, and n-heptane are preferable.Regarding unsaturated hydrocarbon, 2-methyl-2-butene,2-methyl-1-pentene, 2-methyl-2-pentene, 3-ethyl-2-butene,2,3-dimethyl-2-butene, 2,4,4-trimethyl-1-pentene, and2,4,4-trimethyl-2-pentene are preferable.

Among these, in terms of stability, 2-methyl-1-pentene,2-methyl-2-pentene, 3-ethyl-2-butene, 2,3-dimethyl-2-butene,2,4,4-trimethyl-1-pentene, 2,4,4-trimethyl-2-pentene, N-methylpyrrole,and 2-propyne-1-ol are further preferable.

When the solvent composition of the present invention is in contact withcopper or a copper alloy, it may contain nitro compounds and triazolesin order to avoid corrosion of the above metals.

A content of the other components in the solvent composition of thepresent invention is appropriately regulated depending on types of theother components in the range in which the effect of the presentinvention is not impaired. A proportion of the content in a case ofcontaining the other components is preferably about 1 mass % or less andmore preferably 0.1 mass % or less for each of the components to thetotal amount of the solvent composition. Further, a total of the contentof the other components is preferably 10 mass % or less, and morepreferably 1 mass % or less.

The solvent composition of the present invention is a stable solventcomposition which is excellent in solubility of various organicsubstances and excellent in detergency and has a sufficient dryingproperty, and has no adverse effect on a global environment and isstabilized to suppress decomposition, and the solvent composition ispreferably used for cleaning uses such as degreasing cleaning, fluxcleaning, precision cleaning, and dry cleaning. In addition, the solventcomposition of the present invention can be used in uses for which acoating film-forming composition is produced by dissolving a lubricantsuch as a silicone-based lubricant or a fluorine-based lubricant, anantirust made from a mineral oil or a synthetic oil, a moisture-proofcoating agent for conducting water repellent treatment, or anantifouling coating agent such as a fingerprint removing/preventingagent for conducting antifouling treatment and a coating film is formedby applying the coating film-forming composition on an article surface.Moreover, the solvent composition of the present invention is suitablealso as a heat transfer fluid for heating or cooling an article.

The articles to which the solvent composition of the present inventionis applicable can be widely used for electronic components such as acapacitor, a diode, and a substrate on which these have been mounted,optical components such as a lens and a polarizing plate, automotiveparts such as a fuel injection needle to be used for an engine unit anda gear of a drive unit in an automobile, parts of a drive unit to beused for an industrial robot, machine parts such as exterior parts, acarbide tool to be used for a machine tool such as a cutting tool, andthe like. Moreover, as materials to which the solvent composition of thepresent invention is applicable, a wide range of materials such asmetal, plastic, elastomer, glass, ceramics, and fabric can be cited, andamong them, the solvent composition is suitable for metals such as iron,copper, nickel, gold, silver, and platinum, a sintered metal, glass, afluorocarbon resin, and engineering plastic such as PEEK.

<Cleaning Method>

A cleaning method of the present invention is a method of cleaningextraneous matter adhering to an article to be cleaned by using theabove-described solvent composition of the present invention, and ischaracterized by bringing the solvent composition of the presentinvention and the article to be cleaned into contact with each other.

In the cleaning method of the present invention, as the extraneousmatter to be removed by cleaning, there can be cited flux; processingoils such as a cutting oil, a quenching oil, a rolling oil, alubricating oil, a machine oil, a presswork oil, a stamping oil, adrawing oil, an assembly oil, and a wire drawing oil; a release agent;dust, and the like adhering to various articles to be cleaned. Becausethe present solvent composition is more excellent in solubility of theprocessing oil compared with HFC and HFE which are conventional solventcompositions, and the like, it is preferably used for cleaning of theprocessing oil.

Further, the solvent composition of the present invention is applicableto cleaning of the articles to be cleaned made of various materials suchas metal, plastic, elastomer, glass, ceramics, and composite materialsof these, and a fabric made of natural fiber or synthetic fiber. Here,as a more specific example of the articles to be cleaned, there can becited fiber products, medical appliances, electric equipment, precisioninstruments, optical articles, their parts, and the like. As a specificexample of the electric equipment, the precision instruments, theoptical articles, and their parts, there can be cited an IC, acapacitor, a printed-circuit board, a micromotor, a relay, a bearing, anoptical lens, a glass substrate, and the like.

The cleaning method of the article to be cleaned using the solventcomposition of the present invention is not particularly limited exceptto bring the solvent composition of the present invention and thearticle to be cleaned into contact with each other. The contact makes itpossible to remove dirt adhering to a surface of the article to becleaned. As a specific cleaning method, for example, it is sufficient toemploy manual cleaning, immersion cleaning, spray cleaning,immersion-oscillation cleaning, immersion ultrasonic cleaning, steamcleaning, methods by combining these, and the like. Cleaning conditionssuch as contact time, the number of times, and a temperature of thesolvent composition of the present invention at a time of cleaning inthese cleaning methods may be appropriately selected depending on thecleaning methods. Further, also regarding a cleaning apparatus, thepublicly known one can be appropriately selected depending on each ofthe cleaning methods. As long as the solvent composition of the presentinvention is used for these cleaning methods, it is possible torepeatedly use it for a long period while maintaining detergency withalmost no decomposition of the components.

The cleaning method of the present invention is applicable to, forexample, a cleaning method having a solvent contact step in which thearticle to be cleaned is brought into contact with a liquid-phasesolvent composition and a steam contact step in which after the solventcontact step, the article to be cleaned is exposed to steam generated byevaporating the solvent composition. As the cleaning apparatusapplicable to such a cleaning method and the cleaning methods, forexample, a cleaning method and a cleaning apparatus indicated inInternational Publication WO 2008/149907 can be cited.

The FIGURE is a view schematically illustrating one example of acleaning apparatus similar to the cleaning apparatus which carries outthe cleaning method having the above-described solvent contact step andsteam contact step and is indicated in International Publication WO2008/149907. A cleaning apparatus 10 includes a cleaning tank 1, a rinsetank 2, and a steam generation tank 3 in each of which a solventcomposition L is housed. Moreover, the cleaning apparatus 10 includes,above these tanks, a steam zone 4 which is filled with steam generatedfrom the solvent composition L, cooling tubes 9 which cool the steam,and a water separation tank 5 for subjecting the solvent composition Lobtained by being condensed by the cooling tubes 9 and water adhering tothe cooling tubes to a stationary separation. In actual cleaning, anarticle to be cleaned D is put in a dedicated jig or basket, or thelike, and the cleaning is completed while moving the article to becleaned D in order of the cleaning tank 1, the rinse tank 2, and a steamzone 43 immediately above the steam generation tank 3 in the cleaningapparatus 10.

A heater 7 and an ultrasonic vibrator 8 are included in a lower portionof the cleaning tank 1. In the cleaning tank 1, a temperature of thesolvent composition L is raised by heating with the heater 7, physicalforce is imparted to the article to be cleaned D by cavitation generatedby the ultrasonic vibrator 8 while controlling a constant temperature,and dirt adhering to the article to be cleaned D is removed by cleaning.At this time, as the physical force, other than an ultrasonic wave, anymethod which has been employed for previous cleaning machines, such asoscillation or a submerged jet of the solvent composition L, may beused. Note that in the cleaning of the article to be cleaned D in thecleaning tank 1, the ultrasonic vibration is not essential, and thecleaning may be performed without the ultrasonic vibration as necessary.

In the rinse tank 2, by immersing the article to be cleaned D in thesolvent composition L, dirt components adhering to the article to becleaned D in a state of dissolving in the solvent composition L areremoved. The cleaning apparatus 10 has a design in which an overflow ofthe solvent composition L housed in the rinse tank 2 flows into thecleaning tank 1. Further, the cleaning tank 1 includes a pipe 11 whichfeeds the solvent composition L to the steam generation tank 3 in orderto prevent a solution level from becoming equal to or more than apredetermined height.

In a lower portion of the steam generation tank 3, a heater 6 whichheats the solvent composition L in the steam generation tank 3 isincluded. The solvent composition L housed in the steam generation tank3 is boiled by heating with the heater 6, part or the whole of itscomposition becomes steam to rise upward as illustrated by arrows 13,and the steam zone 43 filled with the steam is formed immediately abovethe steam generation tank 3. The article to be cleaned D for which thecleaning in the rinse tank 2 has been completed is transported to thesteam zone 43 and cleaned by the steam through an exposure to the steam(steam contact step).

Further, in the cleaning apparatus 10, an upper space of the tanks isused in common as the steam zone 4. The steam generated from thecleaning tank 1, the rinse tank 2, and the steam generation tank 3 iscollected from the steam zone 4 as the solvent composition L by beingcooled and condensed by the cooling tubes 9 provided in an upper portionof a wall surface of the cleaning apparatus 10. Thereafter, theaggregated solvent composition L is housed in the water separation tank5 via a pipe 14 connecting the cooling tubes 9 and the water separationtank 5. In the water separation tank 5, water mixing in the solventcomposition L is separated. The solvent composition L from which thewater has been separated is returned to the rinse tank 2 through a pipe12 connecting the water separation tank 5 and the rinse tank 2. In thecleaning apparatus 10, such a mechanism allows a reduction in anevaporation loss of the solvent composition.

When cleaning is performed in the cleaning apparatus 10 by using thesolvent composition of the present invention, a temperature of thesolvent composition of the present invention in the cleaning tank 1 ispreferably set to 25° C. or more and less than the boiling point of thesolvent composition. As long as the temperature is in theabove-described range, it is possible to easily perform the degreasingcleaning of a processing oil or the like, and a cleaning effect by theultrasonic wave is high. Further, a temperature of the solventcomposition of the present invention in the rinse tank 2 is preferably10 to 45° C. As long as the temperature is in the above-described range,a difference between a temperature of the article and a temperature ofthe steam of the solvent composition can be obtained sufficiently in asteam cleaning step, and therefore a sufficient amount of the solventcomposition can be condensed on an article surface for steam cleaning,thereby resulting in a high rinsing effect. In addition, the temperatureof the solvent composition of the present invention in the cleaning tank1 is preferably higher than the temperature of the solvent compositionin the rinse tank 2 in terms of detergency.

<Dry Cleaning Method>

Next, a case of using the solvent composition of the present inventionfor removal cleaning of dirt of various clothing will be described. Thesolvent composition of the present invention is suitable as a cleaningsolvent for the clothing, namely, a dry cleaning solvent.

There can be cited cleaning and removing of dirt adhering to clothingsuch as a shirt, a sweater, a jacket, a skirt, trousers, a windbreaker,gloves, a muffler, and a stole, as a dry cleaning application using thesolvent composition of the present invention.

Moreover, the solvent composition of the present invention is applicableto dry cleaning of the clothing made of fibers such as cotton, hemp,wool, rayon, polyester, acryl, and nylon.

Further, it is found that since HCFO-1233yd included in the solventcomposition of the present invention includes a chlorine atom in itsmolecule, it has high solubility of the dirt and has cleaning powernearly equal to that of HCFCs such as HCFC-225(dichloropentafluoropropane) having a wide range of solvency, withrespect to oil and fat dirt.

Moreover, when the solvent composition of the present invention is usedas the dry cleaning solvent, it is possible to compound soap in order toenhance the ability to remove water-soluble dirt such as sweat or mud,and to use the resultant product as a dry cleaning solvent composition.The soap indicates a surfactant to be used for the dry cleaning, and acationic, nonionic, anionic, or ampholytic surfactant or the like ispreferably used. It is found that since HCFO-1233yd has a chlorine atomin its molecule, it has a wide range of solubility to various organiccompounds, and it is not required to optimize the soap depending on thesolvent as HFEs and HFCs are required, which allows use of varioussoaps. Hence, the dry cleaning solvent composition using the solventcomposition of the present invention can include at least one type ofthe surfactant selected from a group consisting of the cationicsurfactant, the nonionic surfactant, the anionic surfactant, and theampholytic surfactant.

As a specific example of the soaps, there can be cited a quaternaryammonium salt such as dodecyldimethylammonium chloride ortrimethylammonium chloride as the cationic surfactant. There can becited a surfactant such as polyoxyalkylene nonylphenyl ether,polyoxyalkylene alkyl ether, fatty acid alkanolamide, glycerin fattyacid ester, sorbitan fatty acid ester, sucrose fatty acid ester,propylene glycol fatty acid ester, or ester of phosphoric acid and fattyacid as the nonionic surfactant. There can be cited an alkyl sulfatesuch as a polyoxyethylene alkyl sulfate, a carboxylate such as a fattyacid salt (so-called soap), or a sulfonate such as an α-olefin sulfonateor a lauryl sulfate as the anionic surfactant. There can be cited abetaine compound such as alkylbetaine as the ampholytic surfactant.

A proportion of the content of the soap in the dry cleaning solventcomposition is 0.01 to 10 mass %, preferably 0.1 to 5 mass %, andfurther preferably 0.2 to 2 mass % to a total amount of the solventcomposition included in the dry cleaning solvent composition.

According to the above-explained cleaning method of the presentinvention, using the above-described solvent composition of the presentinvention suppresses decomposition of the solvent composition and allowsrepeated cleaning for a long period. In addition, as long as the solventcomposition of the present invention is used, it is also possible toappropriately combine regeneration operations such as distillationregeneration and filtration regeneration, gas recovery in whichscattered steam of the solvent composition is recovered, and the likewithout problems.

<Forming Method of Coating Film>

The solvent composition of the present invention can be used for asolvent (dilution coating solvent) for dilution coating of a nonvolatileorganic compound. That is, a method of forming a coating film of thepresent invention is characterized by dissolving a nonvolatile organiccompound in the above-described solvent composition of the presentinvention to prepare a coating film-forming composition and evaporatingthe solvent composition after applying the coating film-formingcomposition on an article to be coated, to form a coating filmconsisting of the nonvolatile organic compound.

Here, the nonvolatile organic compound in the present invention meansthe one which has a boiling point higher than that of the solventcomposition of the present invention and in which the organic compoundstill remains on a surface even after evaporation of the solventcomposition. As the nonvolatile organic compounds, specifically, therecan be cited a lubricant for imparting lubricity to an article, anantirust for imparting an anti-rust effect to metal parts, amoisture-proof coating agent for imparting water repellency to anarticle, an antifouling coating agent such as a fingerprintremoving/preventing agent for imparting antifouling ability to anarticle, and the like. In the method of forming the coating film of thepresent invention, it is preferable to use the lubricant as thenonvolatile organic compound from the viewpoint of solubility.

The lubricant means the one which is used for reducing friction on acontact surface and preventing generation of heat and abrasion damagewhen two members move in a state in which their surfaces are broughtinto contact with each other. The lubricant may be any form of liquid(oil), semisolid (grease), and solid.

As the lubricant, in terms of excellent solubility to HCFO-1233yd, afluorine-based lubricant or a silicone-based lubricant is preferable.Note that the fluorine-based lubricant means a lubricant having afluorine atom in a molecule. Further, the silicone-based lubricant meansa lubricant including silicone.

The lubricant included in the coating film-forming composition may beone or a combination of two or more. Each of the fluorine-basedlubricant and the silicone-based lubricant may be used alone, or theymay be used in combination.

As the fluorine-based lubricant, there can be cited a fluorine-basedoil, fluorine-based grease, or a fluorine-based solid lubricant such asresin powder of polytetrafluoroethylene. As the fluorine-based oil, alow polymer of perfluoropolyether or chlorotrifluoroethylene ispreferable. As commercial products of the fluorine-based oil, forexample, there can be cited product names “Krytox (registered trademark)GPL102” (manufactured by Du Pont Co., Ltd.), “DAIFLOIL #1”, “DAIFLOIL#3”, “DAIFLOIL #10”, “DAIFLOIL #20” “DAIFLOIL #50”, “DAIFLOIL #100”,“DEMNUM S-65” (these are manufactured by Daikin Industries, Ltd.), andthe like.

As the fluorine-based grease, the one in which the fluorine-based oilsuch as the low polymer of perfluoropolyether or chlorotrifluoroethyleneis used as a base oil and powder of polytetrafluoroethylene or otherthickeners are compounded is preferable. As commercial products of thefluorine-based grease, for example, there can be cited product names“Krytox (registered trademark) grease 240AC” (manufactured by Du PontCo., Ltd.), “DAIFLOIL grease DG-203”, “DEMNUM L65”, “DEMNUM L100”,“DEMNUM L200”, (these are manufactured by Daikin Industries, Ltd.),“Sumitec F936” (manufactured by SUMICO LUBRICANT CO., LTD.), “Molykote(registered trademark) HP-300”, “Molykote (registered trademark)HP-500”, “Molykote (registered trademark) HP-870”, “Molykote (registeredtrademark) 6169” (these are manufactured by Dow Corning Toray Co.,Ltd.), and the like.

As the silicone-based lubricant, a silicone oil or silicone grease canbe cited. As the silicone oils, a dimethyl silicone, a methyl hydrogensilicone, a methyl phenyl silicone, a cyclic dimethyl silicone, an aminegroup-modified silicone, a diamine group-modified silicone, and amodified silicone oil in which an organic group has been introduced intoa side chain or a terminal are preferable. As commercial products of thesilicone oil, for example, there can be cited product names “Shin-EtsuSilicone KF-96”, “Shin-Etsu Silicone KF-965”, “Shin-Etsu SiliconeKF-968”, “Shin-Etsu Silicone KF-99”, “Shin-Etsu Silicone KF-50”,“Shin-Etsu Silicone KF-54”, “Shin-Etsu Silicone HIVAC F-4”, “Shin-EtsuSilicone HIVAC F-5”, “Shin-Etsu Silicone KF-56A”, “Shin-Etsu SiliconeKF-995”, “Shin-Etsu Silicone KF-868”, “Shin-Etsu Silicone KF-859” (theseare manufactured by Shin-Etsu Chemical Co., Ltd.), “SH200” (manufacturedby Dow Corning Toray Co., Ltd.), and the like.

As the silicone grease, products in which the various silicone oilscited above are used as a base oil and a thickener such as a metal soapor various additives are compounded are preferable. As commercialproducts of the silicone grease, for example, there can be cited productnames “Shin-Etsu Silicone G-30 Series”, “Shin-Etsu Silicone G-40Series”, “Shin-Etsu Silicone FG-720 Series”, “Shin-Etsu Silicone G-411”,“Shin-Etsu Silicone G-501”, “Shin-Etsu Silicone G-6500”, “Shin-EtsuSilicone G-330”, “Shin-Etsu Silicone G-340”, “Shin-Etsu Silicone G-350”,“Shin-Etsu Silicone G-630” (these are manufactured by Shin-Etsu ChemicalCo., Ltd.), “Molykote (registered trademark) SH33L”, “Molykote(registered trademark) 41”, “Molykote (registered trademark) 44”,“Molykote (registered trademark) 822M”, “Molykote (registered trademark)111”, “Molykote (registered trademark) grease for high vacuum”,“Molykote (registered trademark) heat diffusion compound” (these aremanufactured by Dow Corning Toray Co., Ltd.), and the like.

Further, as the one which can be exemplified as the fluorine-basedlubricant and as the silicone-based lubricant, there can be cited afluorosilicone oil which is a modified silicone oil in which afluoroalkyl group has been substituted for a terminal or a side chain.As commercial products of the fluorosilicone oil, for example, there canbe cited product names “Unidyne (registered name) TG-5601” (manufacturedby Daikin Industries, Ltd.), “Molykote (registered trademark) 3451”,“Molykote (registered trademark) 3452”, (these are manufactured by DowCorning Toray Co., Ltd.), “Shin-Etsu Silicone FL-5”, “Shin-Etsu SiliconeX-22-821”, “Shin-Etsu Silicone X-22-822”, “Shin-Etsu Silicone FL-100”(these are manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.

These lubricants can be used as a coating film for, for example,industrial equipment, tray parts for a CD and a DVD in a personalcomputer and an audiovisual apparatus, household appliances and officeequipment such as a printer, a copier, and a flux device, and the likefor which the fluorine-based lubricant is used normally as the coatingfilm. Further, for example, they can be used for a needle and a cylinderof a syringe, medical tube parts, a metal blade, a catheter, and thelike for which the silicone-based lubricant is used normally as thecoating film.

The antirust means the one which is used for preventing rust of metalmaterials by covering a surface of metals and blocking oxygen from themetal surface which are easily oxidized by oxygen in the air to generaterust. As the antirusts, there can be cited a mineral oil, and syntheticoils such as polyol esters, polyalkylene glycols, and polyvinyl ethers.

The moisture-proof coating agent and the antifouling coating agent arethe ones which are used for imparting a moisture-proof property and anantifouling property to plastic, rubber, metal, glass, a mounted circuitboard, and the like. As product examples of the moisture-proof coatingagent, there can be cited TOPAS 5013, TOPAS 6013, TOPAS 8007(manufactured by Polyplastics Co., Ltd.), ZEONOR 1020R, ZEONOR 1060R(manufactured by Zeon Corporation), Apel 6011T, Apel 8008T,(manufactured by Mitsui Chemicals, Inc.), SFE-DP02H, SNF-DP20H(manufactured by AGC SEIMI CHEMICAL CO., LTD.). As product examples ofthe antifouling coating agent such as a fingerprint preventing agent,there can be cited OPTOOL DSX, OPTOOL DAC (manufactured by DaikinIndustries, Ltd.), Fluoro Surf FG-500 (manufactured by Fluoro TechnologyCo., Ltd.), SR-4000A (manufactured by AGC SEMI CHEMICAL CO., LTD.), andthe like.

The coating film-forming composition is produced normally as acomposition in solution form in which the nonvolatile organic compoundhas been dissolved in the solvent composition of the present invention.A production method of the coating film-forming composition is notparticularly limited as long as it is a method of allowing thenonvolatile organic compound to be uniformly dissolved in the solventcomposition of the present invention in a predetermined proportion. Thecoating film-forming composition basically consists of only thenonvolatile organic compound and the solvent composition of the presentinvention. In the following explanation, the coating film-formingcomposition using the lubricant as the nonvolatile organic compound isreferred to as “lubricant solution”. The coating film-formingcompositions using other nonvolatile organic compounds are also similar.

A content of the lubricant with respect to a total amount of thelubricant solution is preferably 0.01 to 50 mass %, more preferably 0.05to 30 mass %, and further preferably 0.1 to 20 mass %. The remainderexcept the lubricant of the lubricant solution is the solventcomposition. As long as the content of the lubricant is in theabove-described range, a film thickness of a coating film when thelubricant solution is applied and a thickness of a lubricant coatingfilm after drying are easily regulated in a proper range.

A content of each of the nonvolatile organic compounds such as theantirust, the moisture-proof coating agent, and the antifouling coatingagent with respect to a total amount of each of solutions (coatingfilm-forming compositions) in the coating film-forming compositions suchas an antirust solution, a moisture-proof coating agent solution, and anantifouling coating agent solution is also preferably in the same rangeas the above-described content of the lubricant in the lubricantsolution.

A coating film consisting of the nonvolatile organic compound can beformed on an article to be coated by applying the coating film-formingcomposition containing the above-described solvent composition andnonvolatile organic compound on the article to be coated and evaporatingthe solvent composition from the coating film-forming compositionapplied on the article to be coated.

As the articles to be coated on which the coating film of the lubricant,the antirust, the moisture-proof coating agent, the antifouling coatingagent, or the like is formed, namely, the coating film-formingcomposition each including these is applied, the articles to be coatedmade of various materials such as metal, plastic, elastomer, glass, andceramics can be employed. As specific articles, the articles explainedabove for each of the nonvolatile organic compounds can be cited.

As an applying method of the coating film-forming composition, forexample, there can be cited applying by using a brush, applying byspraying, applying by immersing the articles in the coating film-formingcomposition, an applying method of bringing the coating film-formingcomposition into contact with an inner wall of a tube or a needle bypumping up the coating film-forming composition, or the like.

As a method of evaporating the solvent composition from the coatingfilm-forming composition, a publicly known drying method can be cited.As the drying method, for example, air drying, drying by heating, or thelike can be cited. A drying temperature is preferably 20 to 100° C.

In the method of forming the coating film of the present inventionexplained above, either in a state of the solvent composition of thepresent invention before dissolving these lubricant, antirust,moisture-proof coating agent, and antifouling coating agent, and thelike, or in a state of the above-described coating film-formingcomposition, the use is possible with almost no decomposition in storageor in use.

<Heat Transfer Fluid and Heat Cycle System>

The solvent composition of the present invention can be used as aworking fluid (heat transfer fluid) for a heat cycle system. That is,the present invention provides the heat transfer fluid including thesolvent composition of the present invention. The heat transfer fluid ofthe present invention is applicable to the heat cycle system by whichmaterials are heated or cooled.

As the heat cycle systems, there can be cited a Rankine cycle system, aheat pump cycle system, a refrigeration cycle system, a heat transportsystem, a secondary refrigerant cooling system, and the like.Hereinafter, as one example of the heat cycle system, the refrigerationcycle system will be explained.

The refrigeration cycle system is a system in which the working fluidremoves heat energy from a load fluid in an evaporator, thereby coolingthe load fluid and cooling it to lower temperature. The refrigerationcycle system is a system constituted of a compressor which compresses aworking fluid vapor A to make it into a working fluid vapor B at hightemperature and high pressure, a condenser which cools and liquefies thecompressed working fluid vapor B to make it into a working fluid C atlow temperature and high pressure, an expansion valve which expands theworking fluid C emitted from the condenser to make it into a workingfluid D at low temperature and low pressure, an evaporator which heatsthe working fluid D emitted from the expansion valve to make it into theworking fluid vapor A at high temperature and low pressure, a pump whichsupplies a load fluid E to the evaporator, and a pump which supplies afluid F to the condenser.

The heat transfer fluid of the present invention may include a componentother than the solvent composition of the present invention in a rangein which the effect of the present invention is not impaired, andpreferably consists of only the solvent composition of the presentinvention. To the heat transfer fluid of the present invention, alubricating oil can be added. For the lubricating oil, a publicly knownlubricating oil to be used for the heat cycle system is used. As thelubricating oils, there can be cited an oxygenated synthetic oil(ester-based lubricating oil, ether-based lubricating oil, and thelike), a fluorine-based lubricating oil, a mineral oil, ahydrocarbon-based synthetic oil, and the like.

Moreover, the heat transfer fluid of the present invention is alsoapplicable to a secondary circulation cooling system. The secondarycirculation cooling system is a system having a primary cooling devicewhich cools a primary refrigerant consisting of ammonia or a hydrocarbonrefrigerant, a secondary circulation cooling device which cools anarticle to be cooled by circulating a secondary refrigerant forsecondary circulation cooling system (hereinafter, referred to as“secondary refrigerant”), and a heat exchanger which exchanges heatbetween the primary refrigerant and the secondary refrigerant and coolsthe secondary refrigerant. This secondary circulation cooling systemallows cooling of the article to be cooled. The heat transfer fluid ofthe present invention is suitable for use as the secondary refrigerant.

EXAMPLES

Hereinafter, the present invention will be explained in detail byexamples. The present invention is not limited to these examples.Examples 1 to 17 are the examples of the solvent composition of thepresent invention, and Examples 18 to 21 are comparative examples.

Production Example: Production of HCFC-244ca

In a two-liter four-necked flask in which a glass distillation column (ameasured value of five stages in the number of stages) packed with anagitator, a Dimroth, a cooler, and a Rasching ring was placed, 1204 g(9.12 mol) of 2,2,3,3-tetrafluoropropanol (TFPO) and 12 g (0.17 mol) ofN,N-dimethylformamide (DMF) were added. 1078 g (9.12 mol) of thionylchloride was dropped and agitated at a normal temperature for 12 hours.A reactor was heated to 100° C., and reactive distillation was performedat a ratio of 5/1 of reflux time/distillation time by using a refluxtimer. Distilled HCFC-244ca was neutralized by a 20 mass % aqueouspotassium hydroxide solution. Recovered HCFC-244ca (purity 100%) was 979g (6.50 mol).

Production Example: Production of HCFO-1233yd and1-chloro-3,3-difluoro-1-propyne

2000 g of HCFC-244ca was used as a raw material, 19.9 g of tetra-n-butylammonium chloride was put in, a reaction temperature was kept at 50° C.,and 2792 g of a 40 mass % aqueous potassium hydroxide solution wasdropped over 30 minutes. Thereafter, a reaction was continued for 52hours, and an organic layer was recovered. The recovered organic layerwas refined, resulting in obtaining 1520 g of purity 100 mass %HCFO-1233yd(Z) (hereinafter, simply referred to as “HCFO-1233yd(Z)”),140 g of purity 100 mass % HCFO-1233yd(E) (hereinafter, simply referredto as “HCFO-1233yd(E)”), and 17 g of a mixture containing 5 mass %1-chloro-3,3-difluoro-1-propyne (the remainder is 95 mass %HCFO-1233yd(E). hereinafter, referred to as “mixture (X)”). This testwas repeatedly performed to produce a required amount of each ofHCFO-1233yd and 1-chloro-3,3-difluoro-1-propyne.

Examples 1 to 17: Production of Solvent Composition (Example)

100 g each of solvent compositions containing HCFO-1233yd(Z) and/orHCFO-1233yd(E), and 1-chloro-3,3-difluoro-1-propyne as a stabilizer isprepared so as to each become a proportion of a content presented inTable 1 by using HCFO-1233yd(Z), HCFO-1233yd(E), and the mixture (X)obtained in the above. Numeric values of HCFO-1233yd(Z), HCFO-1233yd(E),and 1-chloro-3,3-difluoro-1-propyne presented in Table 1 are each theproportion (mass %) of the content of each of the components to a totalof the content of HCFO-1233yd and the content of1-chloro-3,3-difluoro-1-propyne. Note that the solvent compositions inExamples 1 to 17 are each a solvent composition consisting of onlyHCFO-1233yd and 1-chloro-3,3-difluoro-1-propyne.

Examples 18 to 21: Production of Solvent Composition (ComparativeExample)

Solvent compositions each including HCFO-1233yd(Z) and HCFO-1233yd(E) inthe proportion presented in Table 1 and each consisting of onlyHCFO-1233yd are each produced by using HCFO-1233yd(Z) and HCFO-1233yd(E)obtained in the above.

(Test Example 1: Stability Test)

The obtained solvent compositions in Examples 1 to 21 are retained at50° C. for three days. Chlorine ion concentrations immediately after thepreparation (before the test) and after the retention (after the test)are measured, and stability is evaluated by the following index. Table 1presents the results. Note that any of concentrations in the index ofthe evaluation is a chlorine ion concentration.

<Index of Evaluation>

“S (excellent)”: less than 10 mass ppm

“A (good)”: 10 mass ppm or more and less than 50 mass ppm

“B (slightly poor)”: 50 mass ppm or more and less than 100 mass ppm

“x (poor)”: 100 mass ppm or more

In the chlorine ion concentration measurement, 40 g of each of thesolvent compositions and 40 g of ion-exchange water are put in a 200mL-capacity separatory funnel, shaken for one minute, and thereafterleft still, and an upper-layer aqueous phase obtained by a two-layerseparation is separately collected, and the chlorine ion concentrationof the aqueous phase is measured by an ion chromatograph (model number:ICS-1000, manufactured by Dionex Corporation).

Test Example 2: Drying Property Test

A drying property is evaluated based on how traces remain when one dropof each of the solvent compositions in Examples 1 to 21 is dropped usinga Pasteur pipette and volatilized on a mirror-finished SUS plate under anormal temperature. An index of the evaluation is as follows. Table 1presents the results.

<Index of Evaluation>

“S (excellent): no trace remains due to complete volatilization of thesolvent composition”

“A (good): no trace remains due to almost volatilization of the solventcomposition”

“B (possible): a slight residue is recognized, but there is no practicalproblem”

“x (poor): a visible residue is recognized”

TABLE 1 1-chloro-3,3- HCFO-1233yd(Z) HCFO-1233yd(E) difluoro-1-propyneProportion (mass %) of content of each of components to Stability totalof content of HCFO-1233yd and content of Before After Drying Example1-chloro-3,3-difluoro-1-propyne test test property 1 99.8 0.19 0.01 S AS 2 99.98 0.019 0.001 S S S 3 99.998 0.0019 0.0001 S A S 4 97.9 2.0 0.1S A S 5 97.99 2.00 0.01 S A S 6 97.999 2.000 0.001 S S S 7 97.99992.0000 0.0001 S A S 8 79 20 1 S B S 9 79.9 20.0 0.1 S A S 10 79.99 20.000.01 S A S 11 79.999 20.000 0.001 S S S 12 79.9999 20.0000 0.0001 S A S13 0 99 1 S B S 14 0 99.9 0.1 S A S 15 0 99.99 0.01 S A S 16 0 99.9990.001 S S S 17 0 99.9999 0.0001 S A S 18 100 0 — S x S 19 0 100 — S x S20 98 2 — S x S 21 80 20 — S x S

As can be seen from Table 1, any of the solvent compositions of thepresent invention obtained in Examples 1 to 17 indicates thatHCFO-1233yd can be stably retained. In Examples 18 to 21 as thecomparative examples, it is found that HCFO-1233yd is decomposed to someextent. Further, the solvent compositions of the present inventionobtained in Examples 1 to 17 indicate that no trace remains in thedrying test and it volatilizes similarly to the solvent compositions inExamples 18 to 21 consisting of only HCFO-1233yd.

Test Example 3: Stability Evaluation Test by Accelerated Oxidation Test

Regarding the solvent compositions in Examples 1 to 17 (examples) andExamples 18 to 21 (comparative examples) obtained in the above, anaccelerated oxidation test for confirming stability in a reflux time of48 hours is conducted in conformity to an accelerated oxidation test ofJIS K 1508-1982. That is, in 200 mL of each of the solvent compositions,under a condition in which a test piece of carbon steel for machinestructural use (S20C) is made to coexist in a gas phase and a liquidphase, while passing oxygen bubbles saturated with moisture, light isirradiated by an electric bulb, and reflux is performed for 48 hours byheat generation of the electric bulb.

Chlorine ion concentrations before and after the above-describedaccelerated oxidation test are measured, and the stability is evaluatedby the following index. Further, degrees of a change in test pieceappearance before and after the above-described accelerated oxidationtest are evaluated by the following index. Table 2 presents the results.

<Index of Stability Evaluation>

Any of the following concentrations in the index of the evaluation is achlorine ion concentration.

“S (excellent)”: less than 10 mass ppm

“A (good)”: 10 mass ppm or more and less than 50 mass ppm

“B (slightly poor)”: 50 mass ppm or more and less than 100 mass ppm

“x (poor)”: 100 mass ppm or more

<Index of Test Piece Appearance Evaluation>

“S (excellent)”: there is no change before and after the test.

“A (good)”: a gloss has been slightly lost after the test compared withbefore the test, but there is no practical problem.

“B (slightly poor)”: a surface after the test slightly rusts.

“x (poor)”: rust is recognized on the entire surface of the surfaceafter the test.

Test Example 4: Evaluation of Cleaning Ability

Regarding the solvent compositions in Examples 1 to 17 (examples) andExamples 18 to 21 (comparative examples) obtained in the above, each ofthe following cleaning tests A to D is performed, and Table 2 presentsthe results.

[Cleaning Test A]

After immersing a test piece (25 mm×30 mm×2 mm) of SUS-304 in a productname “Daphne Magplus HT-10” (manufactured by Idemitsu Kosan Co., Ltd.)which is a cutting oil, the test piece is immersed in 50 mL of thesolvent composition in each of the examples for one minute and pulledup, and degrees to which the cutting oil has been removed are observed.Evaluation of detergency is performed in accordance with the followingcriteria.

“S (excellent)”: the cutting oil is completely removed.

“A (good)”: the cutting oil is almost removed.

“B (slightly poor)”: the cutting oil remains in trace amounts.

“x (poor)”: the cutting oil considerably remains.

[Cleaning Test B]

A test is conducted similarly to the cleaning test A except to use aproduct name “Daphne Magplus AM20” (manufactured by Idemitsu Kosan Co.,Ltd.) as a cutting oil, and detergency is evaluated by the samecriteria.

[Cleaning Test C]

A test is conducted similarly to the cleaning test A except to use aproduct name “Daphne Magplus HM25” (manufactured by Idemitsu Kosan Co.,Ltd.) as a cutting oil, and detergency is evaluated by the samecriteria.

[Cleaning Test D]

A test is conducted similarly to the cleaning test A except to use aproduct name “G-6318FK” (manufactured by NIHON KOHSAKUYU CO., LTD.) as acutting oil, and detergency is evaluated by the same criteria.

(Test Example 5: Evaluation of Ability as Dilution Coating Solvent)

The solvent compositions in Examples 1 to 17 (examples) and Examples 18to 21 (comparative examples) obtained in the above are used as dilutioncoating solvents, and coating film-forming compositions (lubricantsolutions) are prepared to evaluate ability.

The solvent composition in each of the examples and a product name“Krytox (registered trademark) GPL102” (manufactured by Du Pont Co.,Ltd., fluorine-based oil) which is a fluorine-based lubricant are mixedwith each other so that a content of the fluorine-based lubricant is 0.5mass % with respect to a total amount of the coating film-formingcomposition, and the coating film-forming compositions are prepared.

Next, on a surface of an aluminum deposited sheet in which aluminum hasbeen deposited on a sheet made of iron, the obtained coatingfilm-forming compositions are each applied in a thickness of 0.4 mm andair-dried under a condition of 19° C. to 21° C., thereby each forming alubricant coating film on the aluminum deposited sheet surface. Theevaluation of the ability as the dilution coating solvents of thesolvent compositions when the lubricant coating films are formed isperformed as follows. Table 2 presents the results.

[Dissolved State]

A dissolved state of the coating film-forming composition using thesolvent composition in each of the examples is visually confirmed to beevaluated by the following criteria.

“S (excellent)”: immediately uniformly dissolved to become transparent.

“A (good)”: if shaken, uniformly dissolved to become transparent.

“B (slightly poor)”: slightly cloudy.

“x (poor)”: cloudy or phase-separated.

[Coating Film State]

A state of the lubricant coating film formed by the coating film-formingcomposition using the solvent composition in each of the examples isvisually confirmed to be evaluated by the following criteria.

“S (excellent)”: a uniform coating film is formed.

“A (good)”: an almost uniform coating film is formed.

“B (slightly poor)”: nonuniformity is partially seen on the coatingfilm.

“x (poor)”: nonuniformity is considerably seen on the coating film.

TABLE 2 Stability by accelerated oxidation test Test piece Ability asdilution Chlorine ion appearance coating solvent concentration aftertest Coating Before After Gas Liquid Detergency Dissolved film Exampletest test phase phase Test A Test B Test C Test D state state 1 S A S AS S S S S S 2 S S S S S S S S S S 3 S A S A S S S S S S 4 S A S A S S SS S S 5 S A S A S S S S S S 6 S S S S S S S S S S 7 S A S A S S S S S S8 S B B B S S S S S S 9 S A S A S S S S S S 10 S A S A S S S S S S 11 SS S S S S S S S S 12 S A S A S S S S S S 13 S B B B S S S S S S 14 S A SA S S S S S S 15 S A S A S S S S S S 16 S S S S S S S S S S 17 S A S A SS S S S S 18 S x x x S S S S S S 19 S x x x S S S S S S 20 S x x x S S SS S S 21 S x x x S S S S S S

It can be said that it is obvious from Table 2 that any of the solventcompositions in the examples is more excellent in stability than thesolvent compositions in the comparative examples even in a case ofperforming the accelerated oxidation test. Further, as presented inTable 2, it is found that the solvent compositions in the examples ofthe present invention are capable of sufficiently cleaning and removingthe cutting oil and have excellent detergency similarly to the solventcompositions in Examples 18 to 21 to which no stabilizer is added in anycleaning test.

Moreover, as present in Table 2, it is obvious that the lubricantsolvents using the solvent compositions of the present invention as thedilution coating solvents are excellent in solubility of the lubricantand capable of simply forming uniform lubricant coating films similarlyto the solvent compositions in Examples 18 to 21 which have nostabilizer in any applying test.

Test Example 5: Evaluation of Detergency and Feeling for Clothing

A white cardigan of wool fabric is cleaned using the solvent compositionof the present invention to evaluate a state of detergency and feelingas follows.

10 L (15 kg) of the solvent composition in Example 6 is prepared at thebeginning. Moreover, 75 g (0.5 mass % with respect to a total amount ofthe solvent composition) of NF-98 (manufactured by NICCA CHEMICAL CO.,LTD.: brand name “NF-98”) is added to the solvent composition as soapand stirred well, to make a test solvent to be used for the cleaningtest.

The above-described cardigan which has been worn and become dirty is cutin half, and one of the ones cut in half is used for the cleaning test.For the test cleaning, a dry cleaning tester (brand name: DC-1A,manufactured by DAIEI KAGAKU SEIKI MFG. CO LTD.) is used, theabove-described test solvent and the article to be cleaned are put in acleaning tank whose capacity is about 11 L, and cleaning is performed ata normal temperature for ten minutes. Thereafter, the cleaned cardiganis taken out of the cleaning tank and sufficiently dried, and thecleaning ability and the feeling are evaluated compared with theremaining half cardigan which has not been cleaned. For comparison, asimilar cleaning test is performed on 1,1,1,3,3-pentafluorobutane(HFC-365mfc) and 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether(HFE-347pc-f) which are conventional cleaning solvents.

The cardigan cleaned by the test solvent based on the solventcomposition in Example 6 has the detergency and the feeling equal tothose when it is cleaned by the conventional cleaning solvents.

A solvent composition of the present invention is a stable solventcomposition which is excellent in solubility of various organicsubstances and excellent in detergency and has a sufficient dryingproperty, and has no adverse effect on a global environment and isstabilized to suppress decomposition. This solvent composition is usefulfor a wide range of industrial uses such as cleaning and applying usesand can be used for articles of various materials such as metal,plastic, and elastomer without giving adverse effects.

What is claimed is:
 1. A solvent composition comprising1-chloro-2,3,3-trifluoro-1-propene and 1-chloro-3,3-difluoro-1-propyne,wherein the 1-chloro-2,3,3-trifluoro-1-propene consists of(Z)-1-chloro-2,3,3-trifluoro-1-propene and(E)-1-chloro-2,3,3-trifluoro-1-propene, and a proportion of a content of(Z)-1-chloro-2,3,3-trifluoro-1-propene to a total amount of1-chloro-2,3,3-trifluoro-1-propene is 80 to 100 mass %.
 2. The solventcomposition according to claim 1, wherein a proportion of a content of1-chloro-3,3-difluoro-1-propyne to a total of a content of the1-chloro-2,3,3-trifluoro-1-propene and a content of the1-chloro-3,3-difluoro-1-propyne is 0.0001 to 0.1 mass %.
 3. The solventcomposition according to claim 1, wherein a proportion of a content of1-chloro-2,3,3-trifluoro-1-propene to a total amount of the solventcomposition is 80 mass % or more.
 4. The solvent composition accordingto claim 1, wherein the 1-chloro-2,3,3-trifluoro-1-propene consists of(Z)-1-chloro-2,3,3-trifluoro-1-propene and(E)-1-chloro-2,3,3-trifluoro-1-propene, and a proportion of a content of(Z)-1-chloro-2,3,3-trifluoro-1-propene to a total amount of1-chloro-2,3,3-trifluoro-1-propene is 90 to 100 mass %.
 5. A cleaningmethod comprising bringing the solvent composition according to claim 1and an article to be cleaned into contact with each other.
 6. Thecleaning method according to claim 5, wherein a processing oil adheringto the article to be cleaned is cleaned.
 7. The cleaning methodaccording to claim 6, wherein the processing oil is at least oneselected from a group consisting of a cutting oil, a quenching oil, arolling oil, a lubricating oil, a machine oil, a presswork oil, astamping oil, a drawing oil, an assembly oil, and a wire drawing oil. 8.The cleaning method according to claim 5, wherein the article to becleaned is clothing.
 9. A method of forming a coating film comprisingdissolving a nonvolatile organic compound in the solvent compositionaccording to claim 1 to prepare a coating film-forming composition andevaporating the solvent composition after applying the coatingfilm-forming composition on an article to be coated, to form a coatingfilm consisting of the nonvolatile organic compound.
 10. A heat transferfluid comprising the solvent composition according to claim
 1. 11. Aheat cycle system using the heat transfer fluid according to claim 10.